US4404344A
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Preparing ethylene polymers using Ziegler catalyst comprising cyclodienyl compound of zirconium
Assignee: BASF SE
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Filing: 1981-02-27
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Granted: 1983-09-13
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Expires: 2001-02-27
Abstract
Abstract The invention relates to a method for preparing polymers of ethylene and propylene, or of copolymers of ethylene and alpha olefins such as propylene 1-butene and 1-hexene or alpha omega dienes such as alpha omega octadiene, respectively, by polymerization within a temperature range from -80° to 150° C. in the presence of a halogen free Ziegler type catalyst system consisting of a cyclopentadienyl compound containing a transition metal and of an aluminum alkyl compound, whereby the polymerization is made in the presence of catalyst system consisting of the following components: (1) a compound containing a transition metal and having the general formula (cyclopentadienyl) n MeY n , in which n is an integer from 1 to 4, Me is a transition metal, preferably zirconium, and Y being selected from the group of hydrogen, a C 1 -C 5 alkyl group or C 1 -C 5 metal alkyl group or of a compound of the following general formula ##STR1## in which R is a C 1 -C 5 alkyl group or C 1 -C 5 metalloalkyl group, and (2) an aluminum containing compound of the alumoxan type having the general formula (R-Al-O) m , in which m is an integer of 1 to 20 and R a C 1 -C 5 alkyl group. Preferably the polymerization is effected in the presence of a catalyst system consisting of bis(cyclopentadienyl)zirconium methyl and an alumoxan of the above mentioned formula in which R is methyl group and m being above 2 and preferably above 5. Preferred copolymers of ethylene are obtained with 0.1 to 10% by weight of 1-butene, 1-hexene and alpha omega dienes such as the octadiene, as well as with propylene.
Inventors
- 👤 Hansjorg W. Sinn
- 👤 Walter O. Kaminsky
- 👤 Hans-Jurgen C. Vollmer
- 👤 Rudiger O. H. H. Woldt
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-27 14:53
CPC Classifications
C; C08; C08F; C08F10/00; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65912; C08F4/6592; C08F4/65922; C08F4/65925; Y; Y10; Y10S; Y10S526/00; Y10S526/904; Y10S526/943
Claims Analysis
Total Claims: 19
Claim 1
Independent Claim
193 words
A process for preparing polymers of ethylene and propylene and of copolymers of ethylene and alpha olefins or alpha omega dienes, respectively by polymerizing the monomer(s) within a temperature range from -80° to 150° C. in the presence of a halogen free Ziegler type catalyst system consisting of a cyclopentadienyl compound containing zirconium and of an aluminum alkyl compound, characterized in that polymerization is made in the presence of catalyst system consisting of the following components: (1) a compound containing zirconium and having the general formula (cyclopentadienyl) n MeY n , in which n is an integer from 1 to 4, Me is zirconium and Y is selected from the group consisting of hydrogen, a C 1 -C 5 alkyl group or C 1 -C 5 metal alkyl group or of a group of the following formula ##STR4## in which R is a C 1 -C 5 alkyl group or a C 1 -C 5 metalloalkyl group, and (2) an aluminum containing compound of the alumoxan type having the formula (R-Al-O) m , in which m is an integer of 1 to 20 and R is a C 1 -C 5 alkyl group.
Claim 2
Dependent Claim
193 words
A process for preparing polymers of ethylene and propylene and of copolymers of ethylene and alpha olefins or alpha omega dienes, respectively by polymerizing the monomer(s) within a temperature range from -80° to 150° C. in the presence of a halogen free Ziegler type catalyst system consisting of a cyclopentadienyl compound containing zirconium and of an aluminum alkyl compound, characterized in that polymerization is made in the presence of catalyst system consisting of the following components: (1) a compound containing zirconium and having the general formula (cyclopentadienyl) n MeY n , in which n is an integer from 1 to 4, Me is zirconium and Y is selected from the group consisting of hydrogen, a C 1 -C 5 alkyl group or C 1 -C 5 metal alkyl group or of a group of the following formula ##STR4## in which R is a C 1 -C 5 alkyl group or a C 1 -C 5 metalloalkyl group, and (2) an aluminum containing compound of the alumoxan type having the formula (R-Al-O) m , in which m is an integer of 1 to 20 and R is a C 1 -C 5 alkyl group.
Claim 3
Dependent Claim
43 words
The method of claim 1, characterized in that the polymerization is effected in the presence of a catalyst system consisting of bis(cyclopentadienyl)zirconium methyl and an alumoxan of the above mentioned formula in which R is a methyl group and m being above 2.
Claim 4
Dependent Claim
30 words
The method of claim 1, characterized in that the atom ratio of Al:Zr of the catalyst system is in the range of about 10:1 to 10 8 :1 during polymerization.
Claim 5
Dependent Claim
23 words
The method of claim 1, characterized in that the polymerization is effected at an aluminum concentration of 10 -6 to 10 -2 mol/liter.
Claim 6
Dependent Claim
20 words
The method of claim 1, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
Claim 7
Independent Claim
149 words
A method for preparing copolymers of ethylene and alpha olefins, characterized in that the polymerization is effected within a temperature range from 20° to 150° C. and with a catalyst consisting of the following components: (1) a compound containing zirconium and having the formula (cyclopentadienyl) n MeY n , in which n is an integer from 1 to 4, Me zirconium, and Y is selected from the group consisting of hydrogen, a C 1 -C 5 alkyl group or C 1 -C 5 metal alkyl group or of a group of the following formula ##STR5## in which R is a C 1 -C 5 alkyl group or C 1 -C 5 metalloalkyl group, and (2) an aluminum containing compound of the alumoxan type having the formula (R-Al-O) m , in which m is an integer of 1 to 20 and R is a C 1 -C 5 alkyl group.
Claim 8
Independent Claim
149 words
A method for preparing copolymers of ethylene and alpha olefins, characterized in that the polymerization is effected within a temperature range from 20° to 150° C. and with a catalyst consisting of the following components: (1) a compound containing zirconium and having the formula (cyclopentadienyl) n MeY n , in which n is an integer from 1 to 4, Me zirconium, and Y is selected from the group consisting of hydrogen, a C 1 -C 5 alkyl group or C 1 -C 5 metal alkyl group or of a group of the following formula ##STR5## in which R is a C 1 -C 5 alkyl group or C 1 -C 5 metalloalkyl group, and (2) an aluminum containing compound of the alumoxan type having the formula (R-Al-O) m , in which m is an integer of 1 to 20 and R is a C 1 -C 5 alkyl group.
Claim 9
Dependent Claim
42 words
The method of claim 6, characterized in that the polymerization is effected in the presence of a catalyst system consisting of bis(cyclopentadienyl)zirconium methyl and an alumoxan of the above mentioned formula in which R is methyl group and m being above 2.
Claim 10
Dependent Claim
42 words
The method of claim 6, characterized in that the polymerization is effected with a major proportion of ethylene and a minor proportion of 0.1 to 10% by weight of a monomer selected from the group consisting of alpha-olefines-, and alpha omega dienes.
Claim 11
Dependent Claim
30 words
The method of claim 2, characterized in that the atom ratio of Al:Zr of the catalyst system is in the range of about 10:1 to 10 8 :1 during polymerization.
Claim 12
Dependent Claim
23 words
The method of claim 2, characterized in that the polymerization is effected in an aluminum concentration of 10 -6 to 10 -2 mol/liter.
Claim 13
Dependent Claim
23 words
The method of claim 3, characterized in that the polymerization is effected at an aluminum concentration of 10 -6 to 10 -2 mol/liter.
Claim 14
Dependent Claim
20 words
The method of claim 2, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
Claim 15
Dependent Claim
20 words
The method of claim 3, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
Claim 16
Dependent Claim
20 words
The method of claim 4, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
Claim 17
Dependent Claim
20 words
The method of claim 9, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
Claim 18
Dependent Claim
20 words
The method of claim 10, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
Claim 19
Dependent Claim
20 words
The method of claim 11, characterized in that polymerization is effected within a temperature range between 20° and 150° C.
References Cited (Backward Citations)
US2924593A
Cited
DE2608933A1
Cited
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1986-09-12 | 1987-03-14 | 1987-09-13 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-09-12 | 1991-03-14 | 1991-09-13 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-09-12 | 1995-03-14 | 1995-09-13 | $7700.00 | Window Closed / Lapsed |